Person: Rodríguez Agarrabeitia, Antonia
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First Name
Antonia
Last Name
Rodríguez Agarrabeitia
Affiliation
Universidad Complutense de Madrid
Faculty / Institute
Óptica y Optometría
Department
Química Orgánica
Area
Química Orgánica
Identifiers
17 results
Search Results
Now showing 1 - 10 of 17
Item Unprecedented induced axial chirality in a molecular BODIPY dye: strongly bisignated electronic circular dichroism in the visible region(Chemical Communications, 2013) Márquez Sánchez-Carnerero, Esther María; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Rodríguez Agarrabeitia, Antonia; Bañuelos Prieto, Jorge; Arbeloa, Teresa; López Arbeloa, Íñigo María; Ortíz García, María Josefa; Moya Cerero, Santiago de laEnantiomeric bis(BODIPYs) 1a and 1b exhibit strong bisignated ECD due to the formation of a stable helical conformation with induced axial chirality, which allows efficient excito coupling of the BODIPY chromophores in the Vis region.Item Coumarin–BODIPY hybrids by heteroatom linkage: versatile, tunable and photostable dye lasers for UV irradiation(Physical Chemistry Chemical Physics, 2015) Esnal, Ixone; Duran-Sampedro, Gonzalo; Rodríguez Agarrabeitia, Antonia; Bañuelos, Jorge; García-Moreno, Inmaculada; Macías, Maria Ángeles ; Peña-Cabrera, Eduardo; López-Arbeloa, Iñigo; De la Moya, Santiago; Ortiz, Maria JoséLinking amino and hydroxycoumarins to BODIPYs through the amino or hydroxyl group lets the easy construction of unprecedented photostable coumarin–BODIPY hybrids with broadened and enhanced absorption in the UV spectral region, and outstanding wavelength-tunable laser action within the green-to-red spectral region (∼520–680 nm). These laser dyes allow the generation of a valuable tunable UV (∼260–350 nm) laser source by frequency doubling, which is essential to study accurately the photochemistry of biological molecules under solar irradiation. The tunability is achieved by selecting the substitution pattern of the hybrid. Key factors are the linking heteroatom (nitrogen vs. oxygen), the number of coumarin units joined to the BODIPY framework and the involved linking positions.Item Spiranic BODIPYs: a ground-breaking design to improve the energy transfer in molecular cassettes(Chemical Communications, 2014) Márquez Sánchez-Carnerero, Esther María; Gartzia-Rivero, Leire; Moreno Jiménez, Florencio; Lora Maroto, Beatriz; Rodríguez Agarrabeitia, Antonia; Ortiz García, María Josefa; Bañuelos Prieto, Jorge; López Arbeloa, Íñigo María; Moya Cerero, Santiago De LaBoosted excitation energy transfer in spiranic O BODIPY/polyarenecassettes, when compared with the parent non-spiranic (flexible) system, is highlighted as a proof for the ability of a new structural design to improve the energy transfer in molecular cassettesItem Development of Geometry-Controlled All-Orthogonal BODIPY Trimers for Photodynamic Therapy and Phototheragnosis(Organic Letters, 2022) Prieto Castañeda, Alejandro; García Garrido, Fernando; Díaz Norambuena, Carolina; Escriche Navarro, Blanca; García Fernández, Alba; Bañuelos, Jorge; Rebollar, Esther; García Moreno, Inmaculada; Martínez Máñez, Ramón; Moya Cerero, Santiago De La; Rodríguez Agarrabeitia, Antonia; Ortiz García, María JosefaWe have established an easy synthetic protocol for selectively developing all-orthogonal BODIPY trimers with unprecedented geometries on the basis of selecting methyl oxidation versus electrophilic formylation of key dimeric precursors. Photophysical characterization together with biological assays unraveled the most suitable BODIPY−BODIPY geometrical arrangements within the trimer, forcing them to serve as molecular platforms for the development of new, advanced heavy-atom-free photosensitizers for photodynamic therapy and phototheragnosis.Item Formylation as a Chemical Tool to Modulate the Performance of Photosensitizers Based on Boron Dipyrromethene Dimers(International Journal of Molecular Sciences, 2023) Díaz Norambuena, Carolina; Avellanal Zaballa, Edurne; Prieto Castañeda, Alejandro; Bañuelos, Jorge; de la Moya, Santiago; Rodríguez Agarrabeitia, Antonia; Moya Cerero, Santiago De La; Ortiz, María J.Heavy-atom-free photosensitizers are envisioned as the next generation of photoactive molecules for photo-theragnosis. In this approach, and after suitable irradiation, a single molecular scaffold is able to visualize and kill tumour cells by fluorescence signalling and photodynamic therapy (PDT), respectively, with minimal side effects. In this regard, BODIPY-based orthogonal dimers have irrupted as suitable candidates for this aim. Herein, we analyse the photophysical properties of a set of formyl-functionalized BODIPY dimers to ascertain their suitability as fluorescent photosensitizers. The conducted computationally aided spectroscopic study determined that the fluorescence/singlet oxygen generation dual performance of these valuable BODIPY dimers not only depends on the BODIPY-BODIPY linkage and the steric hindrance around it, but also can be modulated by proper formyl functionalization at specific chromophoric positions. Thus, we propose regioselective formylation as an effective tool to modulate such a delicate photonic balance in BODIPY-based dimeric photosensitizers. The taming of the excited-state dynamics, in particular intramolecular charge transfer as the key underlying process mediating fluorescence deactivation vs. intersystem crossing increasing, could serve to increase fluorescence for brighter bioimaging, enhance the generation of singlet oxygen for killing activity, or balance both for photo-theragnosis.Item BODIPYs revealing lipid droplets as valuable targets for photodynamic theragnosis(Chemical Communications, 2019) Tabero, Andrea; García-Garrido, Fernando; Prieto Castañeda, Alejandro; Palao, Eduardo; Rodríguez Agarrabeitia, Antonia; García-Moreno, Inmaculada; Villanueva Valdés, Miguel Ángel; Moya Cerero, Santiago De La; Ortiz, María JoséEndowing BODIPY PDT agents with the ability to probe lipid droplets is demonstrated to boost their phototoxicity, allowing the efficient use of highly fluorescent dyes (poor ROS sensitizers) as phototoxic agents. Conversely, this fact opens the way to the development of highly bright ROS photosensitizers for performing photodynamic theragnosis (fluorescence bioimaging and photodynamic therapy) from a single simple agent. On the other hand, the noticeable capability of some of the reported dyes to probe lipid droplets in different cell lines under different conditions reveals their use as privileged probes for advancing the study of interesting lipid droplets by fluorescence microscopy.Item Functionalization of photosensitized silica nanoparticles for advanced photodynamic therapy of cancer(International Journal of Molecular Sciences, 2021) Prieto Montero, Ruth; Prieto Castañeda, Alejandro; Katsumiti, Alberto; Cajaraville, Miren P.; Rodríguez Agarrabeitia, Antonia; Ortiz García, María Josefa; Martínez Martínez, VirginiaBODIPY dyes have recently attracted attention as potential photosensitizers. In this work, commercial and novel photosensitizers (PSs) based on BODIPY chromophores (haloBODIPYs and orthogonal dimers strategically designed with intense bands in the blue, green or red region of the visible spectra and high singlet oxygen production) were covalently linked to mesoporous silica nanoparticles (MSNs) further functionalized with PEG and folic acid (FA). MSNs approximately 50 nm in size with different functional groups were synthesized to allow multiple alternatives of PS-PEG-FA decoration of their external surface. Different combinations varying the type of PS (commercial Rose Bengal, Thionine and Chlorine e6 or custom-made BODIPY-based), the linkage design, and the length of PEG are detailed. All the nanosystems were physicochemically characterized (morphology, diameter, size distribution and PS loaded amount) and photophysically studied (absorption capacity, fluorescence efficiency, and singlet oxygen production) in suspension. For the most promising PS-PEG-FA silica nanoplatforms, the biocompatibility in dark conditions and the phototoxicity under suitable irradiation wavelengths (blue, green, or red) at regulated light doses (10–15 J/cm2) were compared with PSs free in solution in HeLa cells in vitro.Item Exploring BODIPY Derivatives as Singlet Oxygen Photosensitizers for PDT(Photochemistry and Photobiology, 2020) Prieto Moreno, Ruth; Prieto Castañeda, Alejandro; Sola Llano, Rebeca; Rodríguez Agarrabeitia, Antonia; García Fresnadillo, David; López Arbeloa, Íñigo María; Villanueva Oroquieta, Ángeles; Ortíz García, María Josefa; Moya Cerero, Santiago de la; Martínez Martínez, VirginiaThis minireview is devoted to honoring the memory of Dr. Thomas Dougherty, a pioneer of modern photodynamic therapy (PDT). It compiles the most important inputs made by our research group since 2012 in the development of new photosensitizers based on BODIPY chromophore which, thanks to the rich BODIPY chemistry, allows a finely tuned design of the photophysical properties of this family of dyes to serve as efficient photosensitizers for the generation of singlet oxygen. These two factors, photophysical tuning and workable chemistry, have turned BODIPY chromophore as one of the most promising dyes for the development of improved photosensitizers for PDT. In this line, this minireview is mainly related to the establishment of chemical methods and structural designs for enabling efficient singlet oxygen generation in BODIPYs. The approaches include the incorporation of heavy atoms, such as halogens (iodine or bromine) in different number and positions on the BODIPY scaffold, and also transition metal atoms, by their complexation with Ir(III) center, for instance. On the other hand, low‐toxicity approaches, without involving heavy metals, have been developed by preparing several orthogonal BODIPY dimers with different substitution patterns. The advantages and drawbacks of all these diverse molecular designs based on BODIPY structural framework are described.Item Halogen-free photosensitizers based on meso-enamine-BODIPYs for bioimaging and photodynamic therapy(Journal of Materials Chemistry B, 2022) Prieto Montero, Ruth; Díaz Andrés, Aitor; Prieto Castañeda, Alejandro; Tabero Truchado, Andrea; Longarte Aldama, Asier; Rodríguez Agarrabeitia, Antonia; Villanueva Oroquieta, Ángeles; Ortíz García, María Josefa; Montero Santos, Raul; Casanova, David; Martínez Martínez, VirginiaThe search for efficient heavy atom free photosensitizers (PSs) for photodynamic therapy (PDT) is a very active field. We describe herein a simple and easily accessible molecular design based on the attachment of an enamine group as an electron-donor moiety at the meso position of the BODIPY core with different alkylation patterns. The effect of the alkylation degree and solvent polarity on the photophysical properties in terms of splitting absorption bands, fluorescence efficiencies and singlet oxygen production is analyzed in depth experimentally using spectroscopic techniques, including femtosecond and nanosecond transient absorption (fs- and ns-TA) and using computational simulations based on time-dependent density functional theory. The correlation between the theoretical/experimental results permits the rationalization of the observed photophysical behavior exhibited by meso-enamine-BODIPY compounds and the determination of mechanistic details, which rule the population of the triplet state manifold. The potential applicability as a theragnostic agent for the most promising compound is demonstrated through in vitro assays in HeLa cells by analyzing the internalization, localization and phototoxic action.Item Phosphorogenic dipyrrinato-iridium(III) complexes as photosensitizers for photodynamic therapy(Phosphorogenic dipyrrinato-iridium(III) complexes as photosensitizers for photodynamic therapy, 2021) Prieto Castañeda, Alejandro; Lérida Viso, A.; Avellanal Zaballa, Edurne; Sola Llano, rebeca; Bañuelos, Jorge; Rodríguez Agarrabeitia, Antonia; Martínez Mañez, Ramon; Ortiz García, María JosefaWe have designed and synthesized a family of Ir(III) metal complexes coordinated with two cyclometalated bisfluorophenylpyridine ligands and an ancillary dipyrromethene which is functionalized with a mesityl group (Ir(dipy)-1), an α-chloroacetyl ester (Ir(dipy)-2) or a chain containing an ammonium cation (Ir(dipy)-3). The Ir (III) complexes feature a high triplet state population enabling red phosphorescence and efficient singlet oxygen generation. Ir(dipy)-2 and Ir(dipy)-3 are demonstrated to stain cells in both one-photon and two-photon confocal imaging. Moreover, Ir(dipy)-2 and Ir(dipy)-3 produce ROS in cells upon irradiation, inducing cell death by apoptosis. Colocalization studies in SK-Mel-103 cells show that Ir(dipy)-3 is partially accumulated in mitochondria and induces upon irradiation a disruption in their morphology. Overall our studies demonstrate that the prepared Ir(III) act as photosensitizers able to kill cells under irradiation, being suitable candidates for photodynamic therapy applications.